Adhesive agent, adhesive material using the same, and method of use thereof

ABSTRACT

An adhesive agent comprising a condensation resin having a structural unit obtained by polycondensing a polymerizable monomer containing a monomer (A) having 2 or more carboxyl groups and a monomer (B) having 2 or more amino groups, and meeting at least one of the following (1) and (2), and the following (3): 
     (1) at least one selected from the group consisting of the monomer (A), an anhydride of the monomer (A). and the monomer (B) is liquid at 25° C.;
 
(2) the condensation resin has a polyoxyalkanediyl group; and
 
(3) the monomer (A) contains an isophthalic acid.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an adhesive agent capable ofmaintaining adhesiveness even under a high temperature environment, anadhesive material using the agent and a method of using the agent andthe material.

2. Related Background Art

Conventionally, acrylic adhesive agents have been often used as adhesiveagents. Also, a silicone adhesive agent is described in, for example,Patent Literature 1 as a heat resistant adhesive agent.

-   [Patent Literature 1] Japanese Patent Application Laid-Open No.    2009-256542

SUMMARY OF THE INVENTION

However, acrylic adhesive agents are unable to maintain the adhesivenessunder a high temperature environment (e.g., 200° C. or higher), posingproblems such as the occurrence of lifting and peeling.

Silicone adhesive agents also have drawbacks such as high cost and beinglimited as to objects that they can be are applied to (e.g.,adhesiveness to plastic materials such as polyester films and polyimidefilms, etc., is poor).

Thus, the present invention intends to provide a novel adhesive agentcapable of maintaining adhesiveness even under a high temperatureenvironment and a method of using the agent. Further, the presentinvention intends to provide an adhesive material using the adhesiveagent and a method of using the material.

An aspect of the present invention relates to an adhesive agentcomprising a condensation resin having a structural unit obtained bypolycondensing a polymerizable monomer containing a monomer (A) having 2or more carboxyl groups and a monomer (B) having 2 or more amino groups.

Further, the adhesive agent meets at least one of the following (1) and(2), and the following (3):

(1) at least one selected from the group consisting of the monomer (A),an anhydride of the monomer (A), and the monomer (B) is liquid at 25°C.;(2) the condensation resin has a polyoxyalkanediyl group; and(3) the monomer (A) contains an isophthalic acid.

According to the above adhesive agent, high adhesiveness is maintainedeven under a high temperature environment (e.g., 200° C. or higher) andthe occurrence of lifting and peeling is sufficiently suppressed.Further, the above adhesive agent exhibits high adhesiveness toadherends such as plastic materials, etc. Furthermore, the aboveadhesive agent can be repeatedly applied to and peeled from an adherendsince high adhesiveness is maintained even after peeled from theadherend.

In the adhesive agent, the monomer (A) may contain an isophthalic acidor a terephthalic acid. In such a case, the effect of being able toprevent deformation of the adhesive agent when exposed to a hightemperature is achieved.

In the adhesive agent, the molar ratio C₁/C₂ of the content C₁ of theisophthalic acid to the content C₂ of the terephthalic acid in thepolymerizable monomer is preferably 1 to 19, and more preferably 3 to19. When the molar ratio C₁/C₂ is greater than this range, the adhesiveagent tends to easily deform when exposed to a high temperature, whereaswhen the molar ratio C₁/C₂ is smaller than this range, the solubility ina solvent tends to decrease and sufficient adhesiveness tends to bedifficult to achieve.

The adhesive agent preferably meets both the above (1) and (2).According to such an adhesive agent, the adhesiveness is furtherenhanced. Further, such an adhesive agent can be easily applied to anadherend, for example, by depressing at 0 to 50° C.

In the above adhesive agent, the condensation resin preferably containsat least one selected from the group consisting of a polyamide imideresin, a polyimide resin and a polyamide resin.

In the above adhesive agent, the condensation resin is preferably apolyamide resin.

In the above adhesive agent, it is preferable that the structural unitin the above condensation resin has the polyoxyalkanediyl group. Inother words, it is preferable that the polyoxyalkanediyl group in theabove (2) be contained in the above structural unit.

In the above adhesive agent, it is preferable that the structure derivedfrom the above monomer (B) in the structural unit have thepolyoxyalkanediyl group. More specifically, it is preferable that thepolyoxyalkanediyl group in the above (2) be contained in the structurederived from the monomer (B) in the above structural unit.

In the adhesive agent, the above polymerizable monomer preferablycontains a monomer (b-1) having a polyoxyalkanediyl group and 2 or moreamino groups in a proportion of 2 to 8 mol % based on the total amountof the monomer (A) and the monomer (B).

Another aspect of the present invention relates to an adhesive agentcontaining a condensation resin selected from the group consisting of apolyamide resin, a polyamide imide resin and a polyimide resin, thecondensation resin having a 1,3-benzenediyl group and apolyoxyalkanediyl group.

In the adhesive agent, the condensation resin may be those containing anisophthalic acid unit. Further, the condensation resin may furthercontain a terephthalic acid unit.

In the adhesive agent, the ratio C₁/C₂ of the content C₁ of theisophthalic acid unit to the content C₂ of the terephthalic acid unit inthe condensation resin is preferably a molar ration of 1 to 19, and morepreferably 3 to 19.

In the above adhesive agent, the condensation resin may be thosecontaining a diamine unit having a polyoxyalkanediyl group.

In the above adhesive agent, the condensation resin may further have a1,4-piperazinediyl group or contain a diamine unit having a1,4-piperazinediyl group.

For example, the adhesive agent of the present invention can be used asa heat resistant adhesive agent which is applied to an adherend andpeeled from the adherend after heated to 200° C. or higher. In otherwords, the adhesive agent of the present invention can also be suitablyused in a process having a step in which the agent is exposed to a hightemperature of 200° C. or higher.

Another aspect of the present invention relates to use of a condensationresin having a structural unit obtained by polycondensing apolymerizable monomer containing a monomer (A) having 2 or more carboxylgroups and a monomer (B) having 2 or more amino groups and meeting atleast one of the following (1) and (2), and the following (3):

(1) at least one selected from the group consisting of the monomer (A),an anhydride of the monomer (A), and the monomer (B) is liquid at 25°C.;(2) the condensation resin has a polyoxyalkanediyl group; and(3) the monomer (A) contains an isophthalic acid, as an adhesive agent.

Yet another aspect of the present invention relates to use of acondensation resin having a structural unit obtained by polycondensing apolymerizable monomer containing a monomer (A) having 2 or more carboxylgroups and a monomer (B) having 2 or more amino groups and meeting atleast one of the following (1) and (2), and the following (3):

(1) at least one selected from the group consisting of the monomer (A),an anhydride of the monomer (A), and the monomer (B) is liquid at 25°C.;(2) the condensation resin has a polyoxyalkanediyl group; and(3) the monomer (A) contains an isophthalic acid, for the production ofan adhesive agent.

Yet another aspect of the present invention relates to use of acondensation resin selected from the group consisting of a polyamideresin, a polyamide imide resin and a polyimide resin, and having a1,3-benzenediyl group and a polyoxyalkanediyl group, as an adhesiveagent.

Yet another aspect of the present invention relates to use of acondensation resin selected from the group consisting of a polyamideresin, a polyamide imide resin and a polyimide resin, and having a1,3-benzenediyl group and a polyoxyalkanediyl group, for the productionof an adhesive agent.

The present invention also provides an adhesive material comprising asubstrate and an adhesive layer containing the above adhesive agentformed on the substrate.

The present invention also provides a method of using an adhesive agent,comprising an application step of applying a second adherend to a firstadherend via an adhesive layer containing the above adhesive agent, aheating step of heating the first adherend and the second adherend undera condition such that a temperature of the adhesive layer is 200° C. orhigher, and a peeling step of peeling the adhesive layer and the secondadherend from the first adherend subjected to the heating step.

In the method of using the adhesive agent, it is preferable to apply thefirst adherend and the second adherend at 0 to 50° C. in the applicationstep.

In the method of using the adhesive agent, it is preferable to peel theadhesive layer and the second adherend from the first adherend at 0 to50° C. in the peeling step.

In the method of using the adhesive agent, the adhesive layer peeled inthe peeling step can be reused in the application step.

The present invention also provides a method of using an adhesivematerial, comprising an application step of applying the adhesivematerial to an adherend so that the adhesive layer is disposed on theside closer to the adherend, a heating step of heating the adherendunder a condition such that the temperature of the adhesive material is200° C. or higher, and a peeling step of peeling the adhesive materialfrom the adherend subjected to the heating step.

In the method of using the adhesive material, it is preferable to applythe adhesive material to the adherend at 0 to 50° C. in the applicationstep.

In the method of using the adhesive material, it is preferable to peelthe adhesive material from the adherend at 0 to 50° C. in the peelingstep.

In the method of using the adhesive material, the adhesive materialpeeled in the peeling step can be reused in the application step.

According to the present invention, a novel adhesive agent capable ofmaintaining adhesiveness even under a high temperature environment and amethod of using the agent are provided. Further, according to thepresent invention, an adhesive material using the adhesive agent and amethod of using the material are provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view showing a preferable embodiment of anadhesive agent of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preferred embodiments of an adhesive agent and an adhesive material ofthe present invention are described below.

(Adhesive Agent)

An adhesive agent of the present embodiment contains a condensationresin having a structural unit obtained by polycondensing apolymerizable monomer containing a monomer (A) having 2 or more carboxylgroups and a monomer (B) having 2 or more amino groups.

Further, the adhesive agent of the present embodiment meets at least oneof the following (1) and (2), and the following (3).

(1) at least one selected from the group consisting of the monomer (A),an anhydride of the monomer (A), and the monomer (B) is liquid at 25°C.;(2) the condensation resin has a polyoxyalkanediyl group; and(3) the monomer (A) contains an isophthalic acid.

According to such an adhesive agent, high adhesiveness is maintainedeven under a high temperature environment (e.g., 200° C. or higher) andthe occurrence of lifting and peeling is significantly suppressed.

The condensation resin does not have to be those produced bypolycondensing the polymerizable monomer but may have a structural unitthat can be formed by polycondensing the polymerizable monomer.

More specifically, to meet the above (1), the condensation resin doesnot necessarily have to be those produced by using a monomer which isliquid at 25° C. (or a monomer of which an anhydride is liquid at 25°C.), but may have a structural unit that can be formed by polycondensinga polymerizable monomer containing a monomer which is liquid at 25° C.(or a monomer of which an anhydride is liquid at 25° C.).

The structural unit in the condensation resin may be a structural unitobtained by polycondensing a single monomer (A) and monomer (B), or astructural unit obtained by polycondensing a plurality of monomers (A)and monomers (B). In the latter case, to meet the above (1), at leastone selected from the group consisting of a plurality of monomers (A),anhydrides thereof and a plurality of monomers (B) may be in the liquidform at 25° C.

The monomer (A) and the monomer (B) which can form the structural unitcan be confirmed by the following method. More specifically, a compoundhaving 2 or more carboxyl groups and a compound having 2 or more aminogroups, produced when the above structural unit is hydrolyzed, can beused as the monomer (A) and the monomer (B), respectively.

For example, the structural unit represented by the following formula(I-1) can be referred to as the structural unit obtained bypolycondensing the monomers represented by the following formula (A-1)and the monomer represented by the following formula (B-1). In theformulae, R¹ and R² represent a bivalent organic group.

To meet the above (1) for the structural unit represented by the formula(1-1), at least one of the monomer represented by the formula (A-1) andthe monomer represented by the formula (B-1) may be in the liquid format 25° C.

For example, the structural unit represented by the following formula(I-2) can be referred to as the structural unit obtained bypolycondensing the monomers represented by the following formula (A-2)and the monomer represented by the following formula (B-1). In theformulae, R³ represents a tervalent organic group.

To meet the above (1) for the structural unit represented by the formula(1-2), at least one selected from the group consisting of the monomerrepresented by the formula (A-2), the monomer represented by the formula(B-1) and the anhydride represented by the following formula (A-2′) maybe in the liquid form at 25° C.

Further, for example, the structural unit represented by the followingformula (1-3) can be referred to as the structural unit obtained bypolycondensing the monomers represented by the following formula (A-3)and the monomer represented by the above formula (B-1). In the formulae,R⁴ represents a quadrivalent organic group.

To meet the above (1) for the structural unit represented by the formula(I-3), at least one selected from the group consisting of the monomerrepresented by the formula (A-3), the monomer represented by the formula(B-1) and the anhydride represented by the following formula (A-3′) maybe in the liquid form at 25° C.

Examples of the monomer (A) include the monomer having 2 carboxyl groups(the monomer represented by the formula (A-1)), the monomer having 3carboxyl groups (the monomer represented by the formula (A-2)), and themonomer having 4 carboxyl groups (the monomer represented by the formula(A-3)).

Examples of the monomer having 2 carboxyl groups include alkylenedicarboxylic acids such as oxalic acid, malonic acid, succinic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,sebacic acid, 1,9-nonanedicarboxylic acid, dodecanedioic acid,tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid;aromatic dicarboxylic acids such as phthalic acid, terephthalic acid,isophthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalene dicarboxylic acid,acenaphthylene-5,6-dicarboxylic acid, pyridine-2,3-dicarboxylic acid,pyridine-2,6-dicarboxylic acid, 1H-imidazole-4,5-dicarboxylic acid,1H-pyrrole-2,4-dicarboxylic acid, furan-2,5-dicarboxylic acid,thiophene-2,5-dicarboxylic acid; dicarboxylic acids having thecyclohexane skeleton such as 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid,3-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid,4-ethylhexahydrophthalic acid, methyl norbornene-2,3-dicarboxylic acid;and dicarboxylic acids having the cyclohexene skeleton such as3-methyl-1,2,3,6-tetrahydrophthalic acid,4-methyl-1,2,3,6-tetrahydrophthalic acid,methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid.

More specifically, examples of R¹ in the formula (1-1) include analkanediyl group, a bivalent alicyclic group and a bivalent aromaticring group.

For the alkanediyl group, an alkanediyl group of 1 to 30 carbon atoms ispreferable, and an alkanediyl group of 1 to 20 carbon atoms is morepreferable. The alkanediyl group may be linear or branched, but it ispreferable that the alkanediyl group be linear.

Specific examples of the alkanediyl group include a methylene group, anethylene group, a propanediyl group, a butanediyl group, a pentanediylgroup, a hexanediyl group, a heptanediyl group, an octanediyl group, anonanediyl group, a decanediyl group, an undecanediyl group, adodecanediyl group, a tridecanediyl group and a hexadecanediyl group.

The bivalent alicyclic group is a non-aromatic saturated or unsaturatedgroup having a carbocyclic structure. The number of carbon atoms of thebivalent alicyclic group is preferably 3 to 20, and more preferably 4 to12. Further, the bivalent alicyclic group preferably has a cyclohexanering.

Examples of the bivalent alicyclic group include a 1,3-cyclohexanediylgroup, a 1,4-cyclohexanediyl group, a 4-alkylcyclohexane-1,2-diyl group,a 3-alkylcyclohexane-1,2-diyl group, a 4,5-dialkylcyclohexane-1,2-diylgroup, a 3,4-dialkylcyclohexane-1,2-diyl group, a norbornanediyl group,a 5-alkylnorbornane-2,3-diyl group, a 3-alkyl-4-cyclohexene-1,2-diylgroup, a 4-alkyl-4-cyclohexene-1,2-diyl group and a4-methyl-3,6-endomethylene-4-cyclohexene-1,2-diyl group.

The alkyl group bonded to the carbocyclic structure of the bivalentalicyclic group is preferably an alkyl group of 1 to 10 carbon atoms,and more preferably an alkyl group of 1 to 5 carbon atoms.

The bivalent aromatic ring group is an aromatic group having a cyclicstructure. For the bivalent aromatic ring group, a bivalent aromaticring group of 6 to 20 carbon atoms is preferable, and a bivalentaromatic ring group of 6 to 10 carbon atoms is more preferable.

Examples of the bivalent aromatic ring group include a benzenediylgroup, a naphthalenediyl group, a biphenyldiyl group, anacenaphthylene-5,6-diyl group, a pyridine-2,3-diyl group, apyridine-2,6-diyl group, a 1H-imidazole-4,5-diyl group, a1H-pyrrole-2,4-diyl group, a furan-2,5-diyl group and athiophene-2,5-diyl group. Examples of the benzenediyl group include a1,2-benzenediyl group, a 1,3-benzenediyl group and a 1,4-benzenediylgroup. Examples of the naphthalenediyl group include a1,2-naphthalenediyl group, a 1,3-naphthalenediyl group, a1,4-naphthalenediyl group, a 1,5-naphthalenediyl group, a1,6-naphthalenediyl group, a 1,7-naphthalenediyl group, a1,8-naphthalenediyl group, a 2,3-naphthalenediyl group, a2,6-naphthalenediyl group and a 2,7-naphthalenediyl group. Examples ofthe biphenyldiyl group include a biphenyl-4,4′-diyl group.

Examples of the monomer having 3 carboxyl groups include aromatictricarboxylic acids such as trimellitic acid; and alicyclictricarboxylic acids such as cyclohexane-1,2,4-tricarboxylic acid.

More specifically, examples of R³ in the formula (I-2) include atervalent alicyclic group and a tervalent aromatic ring group.

For the tervalent alicyclic group, a cyclohexanetriyl group ispreferable, and a cyclohexane-1,2,4-triyl group is more preferable.

Examples of the tervalent aromatic ring group include a benzenetriylgroup and a naphthalenetriyl group, and a benzene-1,2,4-triyl group ispreferable.

Examples of the monomer having 4 carboxyl groups include pyromelliticacid, benzene-1,2,3,4-tetracarboxylic acid,1,2,5,6-naphthalenetetracarboxylic acid,2,3,6,7-naphthalenetetracarboxylic acid,1,2,4,5-naphthalenetetracarboxylic acid,1,4,5,8-naphthalenetetracarboxylic acid,2,3,6,7-anthracenetetracarboxylic acid, phenanthrene1,8,9,10-tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid,3,3′,4,4′-biphenyltetracarboxylic acid,2,2′,3,3′-biphenyltetracarboxylic acid,2,3,3′,4′-biphenyltetracarboxylic acid,3,3′,4,4′-benzophenonetetracarboxylic acid,2,3,2′,3′-benzophenonetetracarboxylic acid,2,3,3′,4′-benzophenonetetracarboxylic acid, 3,3′,4,4′-biphenyl ethertetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether,bis(3,4-dicarboxyphenyl)sulfone,1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid,bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane,1,1-bis(2,3-dicarboxyphenyl)ethane, 1,1-bis(3,4-dicarboxyphenyl)ethane,2,2-bis(3,4-dicarboxyphenyl)propane,2,2-bis(2,3-dicarboxyphenyl)propane,4,4′-(4,4′-isopropylidenediphenoxy)-bis(phthalicacid),p-phenylenebis(trimellitate),bis(3,4-dicarboxyphenyl)dimethylsilane,bis(3,4-dicarboxyphenyl)methylphenylsilane,bis(3,4-dicarboxyphenyl)diphenylsilane,1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane,1,4-bis(3,4-dicarboxyphenyldimethylsilyl)benzene,2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane,2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane,4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide,2,3,5,6-pyridinetetracarboxylic acid,pyrrolidine-2,3,4,5-tetracarboxylic acid,pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylicacid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid,ethylenetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid,1,1,2,2-ethanetetracarboxylic acid, 1,1,2,3-propanetetracarboxylic acid,1,1,6,6-hexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylicacid, 1,2,3,4-cyclopentanetetracarboxylic acid,1,2,3,4-cyclobutanetetracarboxylic acid,decahydronaphthalene-1,4,5,8-tetracarboxylic acid,4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylicacid, cyclopentane-1,2,3,4-tetracarboxylic acid,1,2,3,4-cyclobutanetetracarboxylic acid,bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid,bis(exobicyclo[2.2.1]heptane-2,3-dicarboxylic acid)sulfone,1,2,4,5-tetracarboxycyclohexane,bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid and5,5′-(1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diyl)bis(bicyclo[2.2.1]heptane-2,3-dicarboxylicacid).

More specifically, examples of R⁴ in the formula (1-3) include analkanetetrayl group, a quadrivalent alicyclic group, a quadrivalentaromatic ring group or a quadrivalent heterocyclic group. In otherwords, groups in which 4 hydrogen atoms are removed from alkanes,alicyclic compounds, aromatic compounds or heterocyclic compounds can benamed as examples of R⁴.

The number of carbon atoms of the alkanetetrayl group is preferably 2 to10, and more preferably 2 to 6. Examples of the alkanetetrayl groupinclude an ethane-1,1,2,2-tetrayl group, a propane-1,1,2,3-tetraylgroup, a butane-1,2,3,4-tetrayl group, a hexane-1,1,6,6-tetrayl groupand an ethylenetetrayl group.

The quadrivalent alicyclic group is preferably those of 4 to 50 carbonatoms, and more preferably those of 6 to 30 carbon atoms. Further, it ispreferable that the quadrivalent alicyclic group have a cyclohexanering.

Examples of the quadrivalent alicyclic group include groups in which 4hydrogen atoms are removed from cyclohexane, cyclopentane, cyclobutane,bicyclohexane, decahydronaphthalene, bicyclo[2,2,2]octane,bicyclo[2,2,1]heptane, dimethylhexahydronaphthalene,bicyclo[2,2,2]oct-7-ene,5,5′-(1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diyl)bis(bicyclo[2.2.1]heptane)or bis(bicyclo[2,2,1]heptane)sulfone.

Examples of the quadrivalent aromatic ring group include groups in which4 hydrogen atoms are removed from benzene, naphthalene, anthracene,phenanthrene, perylene, biphenyl, benzophenone, biphenyl ether,diphenylsulfone, trifluoromethyl benzene, diphenylmethane,1,1-diphenylethane, 2,2-diphenylpropane,2,2-bis(4-phenoxyphenyl)propane, bisphenyl benzoate,diphenyldimethylsilane, triphenylmethylsilane, tetraphenylsilane,1,3-diphenyl-1,1,3,3-tetramethyldisiloxane,bis(diphenyldimethylsilyl)benzene, 2,2-diphenylhexafluoropropane,2,2-bis(4-phenoxyphenyl)hexafluoropropane or diphenylsulfide.

Examples of the quadrivalent heterocyclic group include groups in which4 hydrogen atoms are removed from pyridine, pyrazine, thiophene,pyrrolidine or tetrahydrofuran.

Of these monomers (A) and the anhydrides thereof, examples of thecompound that are liquid at 25° C. include 3-methyl hexahydrophthalicanhydride, 4-methyl hexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethyl hexahydrophthalic anhydride,3-methyl-1,2,3,6-tetrahydrophthalic anhydride,4-methyl-1,2,3,6-tetrahydrophthalic anhydride,methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, and5,5′-exo-(1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diyl)bis(bicyclo[2.2.1]heptane-exo-2,3-dicarboxylicacid)dianhydride.

When R¹ in the above formula (I-1) is, for example, a4-alkylcyclohexane-1,2-diyl group, a 3-alkylcyclohexane-1,2-diyl group,a 3-alkyl-4-cyclohexene-1,2-diyl group, a 4-alkyl-4-cyclohexene-1,2-diylgroup, a 4-methyl-3,6-endomethylene-4-cyclohexene-1,2-diyl group(preferably a 4-methylcyclohexane-1,2-diyl group, a3-methylcyclohexane-1,2-diyl group, a 3-methyl-4-cyclohexane-1,2-diylgroup, a 4-methyl-4-cyclohexane-1,2-diyl group, and a4-methyl-3,6-endomethylene-4-cyclohexene-1,2-diyl group), the adhesiveagent according to the present embodiment meets the above (1).

Also, when R⁴ in the above formula (1-3) is, for example,5,5′-exo-(1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diyl)bis(bicyclo[2.2.1]heptane-exo-2,3-diylgroup), the adhesive agent according to the present embodiment meets theabove (1).

The monomer (A) contains an isophthalic acid. The content of theisophthalic acid is preferably 50 to 95 mol %, and more preferably 75 to95 mol %, based on the total amount of the monomer (A).

The monomer (A) may further contain a terephthalic acid. When themonomer (A) contains an isophthalic acid and a terephthalic acid, theeffect of being able to prevent deformation of the adhesive agent whenexposed to a high temperature is achieved.

The molar ratio C₁/C₂ of the content C₁ of the isophthalic acid to thecontent C₂ of the terephthalic acid in the polymerized monomer ispreferably 1 to 19, and more preferably 3 to 19. When the molar ratioC₁/C₂ is greater than this range, the adhesive agent tends to easilydeform when exposed to a high temperature, whereas when the molar ratioC₁/C₂ is smaller than this range, the solubility in a solvent tends todecrease and sufficient adhesiveness tends to be difficult to achieve.

A monomer having 2 amino groups is preferable as the monomer (B), andexamples of such a monomer include aromatic diamines such as2,2-bis[(4-(4-aminophenoxy)phenyl)]propane,bis[4-(3-aminophenoxy)phenyl]sulfone,bis[4-(4-aminophenoxy)phenyl]sulfone,2,2-bis[(4-(4-aminophenoxy)phenyl)]hexafluoropropane,bis[4-(4-aminophenoxy)phenyl]methane, 4,4′-bis(4-aminophenoxy)biphenyl,bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ketone,1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene,2,2′-dimethylbiphenyl-4,4′-diamine,2,2′-bis(trifluoromethyl)biphenyl-4,4′-diamine,2,6,2′,6′-tetramethylbiphenyl-4,4′-diamine,5,5′-dimethyl-2,2′-sulfonyl-biphenyl-4,4′-diamine,(4,4′-diamino)diphenyl ether, (4,4′-diamino)diphenylsulfone,(4,4′-diamino)benzophenone, (3,3′-diamino)benzophenone,(4,4′-diamino)diphenylmethane and (4,4′-diamino)diphenyl ether,(3,3′-diamino)diphenyl ether; alkylene diamines such as ethylenediamineand propylenediamine; polyalkylene oxide diamines such as polyethyleneoxide diamine and polypropylene oxide diamine; aliphatic diamines suchas 1,3-cyclohexanediamine, 1,4-cyclohexanediamine,(4,4′-diamino)dicyclohexylmethane, isophoronediamine,1,4-bisaminopropylpiperazine,[3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)]cyclohexene andbisaminomethylnorbornane; and siloxane diamines such as polydimethylsiloxane diamine.

In other words, examples of R² in the formulae (1-1), (1-2) and (1-3)include an alkanediyl group, a polyoxyalkanediyl group, a bivalentalicyclic group, a bivalent aromatic ring group, a bivalent heterocyclicring group and a polysiloxanediyl group.

For the alkanediyl group in R², an alkanediyl group of 1 to 30 carbonatoms is preferable, and an alkanediyl group of 1 to 20 carbon atoms ismore preferable. The alkanediyl group may be linear or branched, but itis preferably linear.

Examples of the alkanediyl group in R² include a methylene group, anethylene group, a propanediyl group, a butanediyl group, a pentanediylgroup, a hexanediyl group, a heptanediyl group, an octanediyl group, anonanediyl group, a decanediyl group, a undecanediyl group, adodecanediyl group, a tridecanediyl group and a hexadecanediyl group.

For the bivalent alicyclic group in R², an alicyclic group of 3 to 10carbon atoms is preferable, and an alicyclic group of 4 to 8 carbonatoms is more preferable. Also, the bivalent alicyclic group preferablyhas a cyclohexane ring.

Examples of the bivalent alicyclic group in R² include a cyclohexanediylgroup, an alkylcyclohexane-1,4-diyl group, a dialkylcyclohexane-1,4-diylgroup, a norbornanediyl group, an alkylnorbornane-2,3-diyl group, adicyclohexylmethanediyl group, a dicyclohexylpropanediyl group, anisophoronyl group, a bismethylenecyclohexane group, and abismethylenenorbornane group.

The alkyl group bonded to the carbocyclic structure of the bivalentalicyclic group in R² is preferably an alkyl group of 1 to 10 carbonatoms, and more preferably an alkyl group of 1 to 5 carbon atoms.

Examples of the bivalent aromatic ring group in R² include benzenediylgroups (a 1,2-benzenediyl group, a 1,3-benzenediyl group, a1,4-benzenediyl group), naphthalenediyl groups (a 1,2-naphthalenediylgroup, a 1,3-naphthalenediyl group, a 1,4-naphthalenediyl group, a1,5-naphthalenediyl group, a 1,6-naphthalenediyl group, a1,7-naphthalenediyl group, a 1,8-naphthalenediyl group, a2,3-naphthalenediyl group, a 2,6-naphthalenediyl group and a2,7-naphthalenediyl group), a 4,4′-biphenyldiyl group, a3,3′-biphenyldiyl group, a 4,4′-(2,2′-diphenylpropane)diyl group, a3,3′-(2,2′-diphenylpropane)diyl group, a 4,4′-(diphenylsulfone)diylgroup, a 3,3′-(diphenylsulfone)diyl group, a4,4′-(3,3-diphenylhexafluoropropane)diyl group, a3,3′-(3,3-diphenylhexafluoropropane)diyl group, a 4,4′-(diphenylether)diyl group, a 3,3′-(diphenyl ether)diyl group, a4,4′-(diphenylketone)diyl group, a 3,3′-(diphenylketone)diyl group, a4,4′-(2,2′-dimethylbiphenyl)diyl group, a4,4′-(2,2′-bis(trifluoromethyl)biphenyl)diyl group and a4,4′-(2,6,2′,6′-tetramethylbiphenyl)diyl group.

Examples of the bivalent heterocyclic group in R² include a(1,4-dipropylpiperazine)diyl group.

Examples of the polysiloxanediyl group in R² include a polydimethylsiloxanediyl group.

Of these monomers (B), examples of the monomers that are liquid at 25°C. include ethylenediamine, propylenediamine, isophoronediamine,1,4-bis-aminopropylpiperazine,[3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)]cyclohexene, alkyleneoxide diamine, bisaminomethylnorbornane, alkyl diamine, polyalkyleneoxide diamine and siloxane diamine.

When R² in the formulae (I-1), (I-2) and (I-3) is, for example, analkanediyl group, a (1,4-dipropylpiperazine)diyl group, abismethylenenorbornane group or an isophoronyl group, the adhesive agentaccording to the present embodiment meets the above (1).

The condensation resin preferably has a polyoxyalkanediyl group. Thecondensation resin having such a group has reduced Tg, thereby havinggood adhesiveness at a low temperature.

Examples of the polyoxyalkanediyl group herein include the groupsrepresented by the following formula (2). In the formula, n representsan integer of 2 or more and R⁵ represents an alkanediyl group.

A plurality of R⁵s present may be mutually identical or different.

The alkanediyl group in R⁵ may be linear or branched. For the alkanediylgroup in R⁵, an alkanediyl group of 2 to 4 carbon atoms is preferable,and an alkanediyl group of 2 to 3 carbon atoms is more preferable.Examples of the alkanediyl group in R⁵ include an ethylene group, a1,2-propanediyl group, a 1,3-propanediyl group and a 1,4-butanediylgroup.

The n in the formula (2) is preferably 2 to 70, and more preferably 6 to33.

The polyoxyalkanediyl group is preferably a group derived frompolyalkylene oxides such as polyethylene oxide, polypropylene oxide,polybutylene oxide, polytetramethylene oxide, a polyethylene oxidepolypropylene oxide copolymer, a polyethylene glycol polytetramethyleneglycol copolymer, a polypropylene glycol polytetramethylene glycolcopolymer and a polyethylene glycol polypropylene glycolpolytetramethylene glycol copolymer, and more preferably apolyoxyethylene group and a polyoxy-1,2-propanediyl group.

The method for incorporating the above polyoxyalkanediyl group into thecondensation resin is not particularly limited, and examples include amethod wherein a condensation resin such as a polyamide resin, apolyimide resin, a polyamide imide resin, or the like, is modified andthe polyoxyalkanediyl group is thereby incorporated.

Further, it is preferable that the condensation resin has thepolyoxyalkanediyl group in the structural unit, and more preferable thatthe polyoxyalkanediyl group be present in the structure derived from themonomer (B) in the structural unit. More specifically, it is preferablethat at least one of the monomer (A) and the monomer (B) has thepolyoxyalkanediyl group, and more preferable that at least one of themonomers (B) has the polyoxyalkanediyl group.

In the condensation resin, it is preferable that the structure derivedfrom the monomer (B) in the above structural unit has thepolyoxyalkanediyl group.

In other words, it is preferable that the condensation resin have thestructural unit obtained by polycondensing the polymerizable monomerscontaining the monomer (b-1) having the polyoxyalkanediyl group and 2 ormore amino groups.

The content of the monomer (b-1) in the polymerizable monomer ispreferably 0.5 to 20 mol %, more preferably 1 to 10 mol %, and even morepreferably 2 to 8 mol %, based on the total amount of the monomer (A)and the monomer (B). According to the condensation resin having thestructural unit obtained by polycondensing such a polymerizable monomer,an adhesive agent is obtained with far superior adhesiveness to anadherend.

The monomer (b-1) may be polyalkelene oxide diamine, and examples whichcan preferably be used include polypropylene oxide diamine such asJEFFAMINE D-230 (HUNTSMAN, trade name), JEFFAMINE D-400 (HUNTSMAN, tradename), JEFFAMINE D-2000 (HUNTSMAN, trade name) and JEFFAMINE D-4000(HUNTSMAN, trade name); copolymer diamines of polypropylene oxide andpolyethylene oxide such as JEFFAMINE ED-600 (HUNTSMAN, trade name) andJEFFAMINE ED-900 (HUNTSMAN, trade name); polyethylene oxide diamine suchas JEFFAMINE EDR-148 (HUNTSMAN, trade name) and JEFFAMINE EDR-176(HUNTSMAN, trade name); triamines such as JEFFAMINE T-403 (HUNTSMAN,trade name), JEFFAMINE T-3000 (HUNTSMAN, trade name) and JEFFAMINET-5000 (HUNTSMAN, trade name). They may be used either individually, orused in combinations of two or more.

When the monomer (A), which is in liquid form at 25° C. or an anhydridethereof is in liquid form at 25° C., is referred to as the monomer(a-1), and when the monomer (B), which is in liquid form at 25° C., isreferred to as the monomer (b-2), the total content of the monomer (a-1)and the monomer (b-2) in the polymerizable monomer is preferably 15 to60 mol %, more preferably 20 to 50 mol %, and even more preferably 25 to45 mol %, based on the total amount of the monomer (A) and the monomer(B).

As a suitable combination of the polymerizable monomers, it ispreferable that the monomer (A) contains an isophthalic acid, and thatthe monomer (B) contains the monomers (b-1) and (b-2).

Further, another suitable combination is that, preferably, the monomer(A) contains an isophthalic acid and the monomer (a-1), and that themonomer (B) contains the monomer (b-1).

For example, the condensation resin can be obtained by polycondensing apolymerizable monomer containing the monomer (A) and the monomer (B).Alternatively, anhydrides of the monomer (A), esterified products of themonomer (A), acid halides of the monomer (A), or the like, can also beused instead of the monomer (A). The polymerizable monomer may alsocontain other monomers such as diisocyanate compounds, and the like.

The content of the monomer (A) and the monomer (B) in the polymerizablemonomer is preferably 30 mol % or more, more preferably 50 mol % ormore, and even more preferably 70 mol % or more, based on the totalamount of the polymerizable monomer. Also, the content of the monomer(A) and the monomer (B) may be 100 mol %.

The method of polycondensation are not particularly limited but amethod, for example, wherein the above polymerizable monomer isdissolved in a solvent and allowed to react at a reaction temperature of0 to 200° C. for a reaction time of about 1 to 5 hours, can be employed.

Examples of the solvent used for the polycondensation includeN-methylpyrrolidone, N-ethylpyrrolidone, N-methylsuccimide,dimethylfuran, toluene, N,N-dimethylacetamide, hexamethylphosphoricamide and dimethyl sulfoxide. Of these solvents, N-methylpyrrolidone ispreferable, from the perspective of resin solubility.

Further, in polycondensation, accelerating agents such as a catalyst, orthe like, can be used for the purpose of promoting the condensationreaction. The amount of an accelerating agent added is preferably a 0.1to 50 mol equivalent based on 10 mol equivalent of the polymerizablemonomer. Examples of the accelerating agent include inorganic salts suchas lithium chloride, calcium chloride and rhodan calcium; tertial aminessuch as triethylamine and pyridine; quarternary ammonium salts such astetramethyl ammonium chloride, tetraethylammonium bromide andtetra-n-butylammonium bromide.

The condensation resin may be those which are further modified polymersobtained by the polycondensation, and examples include olefin modifiedpolyamide, alkoxy silane modified polyamide, siloxane modifiedpolyimide, epoxy modified polyamide, polycarbonate modified polyamide,olefin modified polyimide, siloxane modified polyimide, epoxy modifiedpolyimide, polycarbonate modified polyimide, siloxane modifiedpolyimide, olefin modified polyamide imide, alkoxysilane modifiedpolyamide imide, siloxane modified polyamide imide, epoxy modifiedpolyamide imide, epoxy modified polyamide imide and polycarbonatemodified polyamide imide.

The condensation resin in the present embodiment may be, for example, apolyamide resin, a polyamide imide resin or a polyimide resin, having a1,3-benzenediyl group and a polyoxyalkanediyl group.

The condensation resin may be those containing an isophthalic acid unit.Such a condensation resin meets at least the above (2) and (3). Further,the condensation resin may further contain a terephthalic acid unit.

In the condensation resin, the molar ratio C₁/C₂ of the content C₁ ofthe isophthalic acid to the content C₂ of the terephthalic acid in thecondensation resin is preferably 1 to 19, and more preferably 3 to 19.

The condensation resin may contain a diamine unit having apolyoxyalkanediyl group. Examples of the diamine unit having apolyoxyalkanediyl group include a polyalkylene oxidediamine unit.Examples of the polyalkylene oxidediamine unit include the monomer unitderived from the monomers given as the examples of the abovepolyalkylene oxidediamine.

The condensation resin may also have a 1,4-piperazinediyl group, orcontain a diamine unit having a 1,4-piperazinediyl group. According tosuch a diamine unit, change in the adhesiveness of the adhesive agentunder a high temperature environment can be further suppressed.

Examples of the diamine unit having a 1,4-piperazinediyl group include a1,4-bis(ω-aminoalkyl)piperazine unit. In the1,4-bis(ω-aminoalkyl)piperazine unit, the number of carbon atoms of theω-aminoalkyl group is preferably 1 to 10, and more preferably 2 to 4.

Examples of the 1,4-bis(co-aminoalkyl)piperazine unit include1,4-bis(3-aminopropyl)piperazine unit, and the like.

In the condensation resin, the ratio C_(B)/C_(A) of the content C_(B) ofthe diamine unit having a polyoxyalkanediyl group to the content C_(A)of the diamine unit having the cyclohexane ring is preferably 0.1 to 40,and more preferably 0.5 to 8, on a molar ratio basis.

The structural unit derived from the monomer (A) in the condensationresin can be referred to as the monomer (A) unit, the structural unitderived from the monomer (B) can be referred to as the monomer (B) unit,and the condensation resin can be referred to as the condensation resincontaining the monomer (A) unit and the monomer (B) unit.

The content of the isophthalic acid unit in the condensation resin ispreferably 25 to 50 mol %, more preferably 25 to 47.5 mol %, and evenmore preferably 37.5 to 47.5 mol %, based on the total amount of themonomer (A) unit and the monomer (B) unit. According to such acondensation resin, change in the adhesiveness under a high temperatureenvironment can be further suppressed.

The content of the diamine unit having a polyoxyalkanediyl group in thecondensation resin is preferably 0.5 to 20 mol %, more preferably 1 to10 mol %, and even more preferably 2 to 8 mol %, based on the totalamount of the monomer (A) unit and the monomer (B) unit. According tosuch a condensation resin, the adhesive agent can be obtained with farsuperior adhesiveness to an adherend.

The content of the diamine unit having a 1,4-piperazinediyl group in thecondensation resin is preferably 15 to 60 mol %, more preferably 20 to50 mol %, and even more preferably 25 to 45 mol %, based on the totalamount of the monomer (A) unit and the monomer (B) unit.

The weight average molecular weight of the condensation resin ispreferably 20000 to 100000, and more preferably 30000 to 60000. In thepresent specification, the weight average molecular weight shows theweight average molecular weight in polystyrene conversion as measured bythe GPC method.

The content of the condensation resin in the adhesive agent of thepresent embodiment is preferably 50 mass % or more, and more preferably70 mass % or more, based on the total amount of the adhesive agent. Whenthe content of the condensation resin is within the above range, higheradhesiveness is achieved while sufficient heat resistance is maintained.Further, the content of the condensation resin may be 96 mass % or less,or 90 mass % or less. The adhesive agent of the present embodiment mayconsist of the condensation resin (in other words, the content of thecondensation resin is 100 mass %). However, the content of thecondensation resin can be beyond the above range as necessary, dependingon the application therefor.

Further, in the adhesive agent of the present embodiment, from theperspective of maintaining good adhesiveness under a high temperatureenvironment, the content of the heat curable resin is preferably 30 mass% or less, and more preferably 20 mass % or less, and even morepreferably the heat curable resin not be contained therein.

In the adhesive agent of the present embodiment, adhesiveness impartingagents such as rosin resins, terpene resins, coumarone resins, phenolresins, styrene resins, aliphatic petroleum resins, aromatic petroleumresins, aliphatic-aromatic copolymer petroleum resins, or the like, maybe added for the purpose of enhancing adhesiveness, to the degree thatthe objective of the present invention is not adversely affected.

(Method of Using Adhesive Agent)

The adhesive agent of the present embodiment can be used in theapplication comprising the following steps (1) to (3), sinceadhesiveness can be maintained even under a high temperatureenvironment.

(1) An application step of applying a second adherend to a firstadherend via an adhesive layer containing the adhesive agent.(2) A heating step of heating the first adherend and the second adherendunder a condition such that the temperature of the adhesive layer is200° C. or higher.(3) A peeling step of peeling the adhesive layer and the second adherendfrom the first adherend subjected to the heating step.

In the application step, for example, an adhesive layer is formed on asurface of the first adherend, the second adherend is disposed on thesurface of the adhesive layer opposite to the first adherend, and thefirst adherend and the second adherend are pressed against each other,making it possible to apply the second adherend to the first adherend.

Alternatively, the adhesive layer is formed on a surface of the secondadherend, the first adherend is disposed on the surface of the adhesivelayer opposite to the second adherend, and the first adherend and thesecond adherend are pressed against each other, making it also possibleto apply the second adherend to the first adherend.

The adhesive layer, for example, can be formed by preparing an adhesivevarnish containing the adhesive agent and a solvent, and applying anddrying the adhesive varnish. The solvent used in the adhesive varnish isnot particularly limited but, due to good solubility of the adhesiveagent, glycol solvents, glycol ether solvents, and glycol ester solventsare preferable.

Examples of the solvent include ethylene glycol, diethylene glycol,triethylene glycol, propylene glycol, ethylene glycol, diethyleneglycol, triethylene glycol, propylene glycol, diethylene glycolmonomethyl ether, triethylene glycol monomethyl ether, propylene glycolmonomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycolmonomethyl ether acetate, PMA (propylene glycol monomethyl etheracetate), diethylene glycol monobutyl ether acetate and diethyleneglycol monoethyl ether acetate. In addition to the above solvents,N-methylpyrrolidone, N-ethylpyrrolidone, N-methylsuccimide,N,N-dimethylacetamide and dimethylformamide may be used. These solventsmay be used individually, or in combinations of two or more.

The adhesive layer in the application step may be those formed byapplying the adhesive varnish to a surface of the first adherend or thesecond adherend and drying, or may be those formed by laminating theadhesive layer formed on the substrate to be described later on asurface of the first adherend or the second adherend and transcribing.

In the application step, for example, the first adherend and the secondadherend may be applied at 0 to 50° C.

In the heating step, the first adherend and the second adherend areheated. The method for heating and purpose of heating are notparticularly limited but the adhesive layer is exposed to a temperatureof 200° C. or higher by said heating. When an adhesive agent with lowheat resistance (for example, acrylic adhesive agents) is subjected tosuch a heating step, adhesiveness is usually not maintained, causinglifting and peeling. However, according to the adhesive layer containingthe adhesive agent of the present embodiment, the adhesiveness ismaintained even when subjected to such a heating step, making itpossible to sufficiently suppress the occurrence of lifting and peeling.

In the heating step, the heated first adherend and the second adherendmay be subjected to a molding process. As the adhesive layer containingthe adhesive agent of the present embodiment has excellent flexibilityand thus sufficiently suppresses the occurrence of lifting and peelingeven when the first adherend and the second adherend are deformed by themolding process.

In the peeling step, the adhesive layer and the second adherend arepeeled from the first adherend. In this step, the adhesive layer and thesecond adherend may be integrally peeled from the first adherend, or maybe peeled independently from the first adherend.

In the peeling step, for example, the adhesive layer and the secondadherend can be peeled from the first adherend at 0 to 50° C.

The adhesive layer peeled in the peeling step can be reused in theapplication step as its adhesiveness is maintained even after beingsubjected to the above heating step.

The first adherend and the second adherend are not particularly limited,and examples include those containing at least one organic materialselected from polyester, polyimide, polyamide, polyether sulfone,polyphenylene sulfide, polyether ketone, polyether ether ketone,triacetyl cellulose, polyetherimide, polyethylene naphthalate,polypropylene, acryl, polystyrene, polycarbonate, and the like. Further,a substrate containing an inorganic material may also be used, andexamples include those containing at least one inorganic materialselected from aluminum, magnesium, titanium, chromium, manganese, iron,nickel, zinc, tin, glass, copper, silicon wafer and alloy.

For the first adherend and the second adherend, materials heat resistantto a temperature of 200° C. or higher may be used, and examples includepolyamide resins such as Nylon 6, Nylon 66 and Nylon 46; polyesterresins such as polyethylene terephthalate, polyethylene naphthalate,polytrimethylene terephthalate, polytrimethylene naphthalate,polybutylene terephthalate and polybutylene naphthalate; polyolefinresins such as polypropylene and polyethylene; acrylic resins, polyimideresins, polyarylate resins or resin mixtures thereof; aluminum,magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin,glass, copper and silicon wafer. Of these materials, polyester resins,polyamide resins, polyolefin resins, polyimide resins, acrylic resins,aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc,tin, glass, copper, and silicon wafer are preferable since they exhibithigh heat resistance.

According to the above method of use, for example, the low rigidityfirst adherend is securely adhered to the second adherend in a hightemperature process, and can be peeled after the process without beingdamaged or deformed.

(Adhesive Material)

FIG. 1 is a schematic view showing a preferable embodiment of anadhesive agent of the present invention. An adhesive agent 1 shown inFIG. 1 is provided with a substrate 10 and an adhesive layer 14containing the adhesive agent formed on the substrate 10.

The substrate is not particularly limited, and examples include thosecontaining at least one organic material selected from polyester,polyimide, polyamide, polyether sulfone, polyphenylene sulfide,polyether ketone, polyether ether ketone, triacetyl cellulose,polyetherimide, polyethylene naphthalate, polypropylene, acryl,polystyrene, polycarbonate, and the like. Also, a substrate containingan inorganic material can be used, and examples include those includingat least one inorganic material selected from aluminum, magnesium,titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper,silicon wafer and alloy.

The adhesive material can be produced, for example, by applying anadhesive varnish containing the adhesive agent and a solvent to thesubstrate and drying to form an adhesive layer. Such a production methodby the casting method is preferable because a flat adhesive layer can beeasily obtained. Examples of the solvent used in the adhesive varnishinclude the same as those described above.

Alternatively, the adhesive material can be produced by laminating andtranscribing to the substrate the adhesive layer formed by applying theadhesive varnish containing the adhesive agent and a solvent to a moldrelease film and drying.

The thickness of the adhesive layer is preferably 0.1 to 100 μm, andmore preferably 1 to 50 μm. The thickness of the adhesive layer can besuitably adjustable depending on the concentration of the adhesive agentin the adhesive varnish and the amount of the adhesive varnish to beapplied.

(Method of Using Adhesive Material)

The adhesive agent of the present embodiment can be used in applicationscomprising the following steps (1) to (3) since adhesiveness can bemaintained even under a high temperature environment.

(1) An application step of applying the adhesive material to an adherendso that the adhesive layer is disposed on the side closer to theadherend.(2) A heating step of heating the adherend under a condition such thatthe temperature of the adhesive material is 200° C. or higher.(3) A peeling step of peeling the adhesive material from the adherendsubjected to the heating step.

In the application step, the adhesive material can be applied to theadherend by depressing the adhesive layer of the adhesive material andthe adherend so that they are in contact. In the application step, thefirst adherend and the second adherend can be applied at any temperaturebut, for example, it is desirable to apply at 0 to 50° C. from theperspective of achieving suitable adhesiveness and work efficiency.

In the heating step, the adherend is heated, and the adhesive layertherewith is simultaneously exposed to a temperature of 200° C. orhigher. When an adhesive agent with low heat resistance (for example,acrylic adhesive agents) is subjected to such a heating step,adhesiveness is not maintained and lifting and peeling are caused.However, according to the adhesive material of the present embodiment,the occurrence of lifting and peeling can be sufficiently suppressedbecause adhesiveness is maintained even when subjected to such a heatingstep.

In the heating step, the heated adherend may be subjected to a moldingprocess. As the adhesive layer containing the adhesive agent of thepresent embodiment has superior flexibility, the occurrence of liftingand peeling is sufficiently suppressed even when the adherend isdeformed by the molding process.

In the peeling step, the adhesive material is peeled from the adherend.In the peeling step, for example, the adhesive material can be peeledfrom the adherend at 0 to 50° C.

The adhesive material peeled in the peeling step can be reused in theapplication step because adhesiveness is maintained even after subjectedto the above heating step.

Examples can be shown of the adherend used in the present method of use,that are identical to the first adherend and the second adherend.

According to the above method of use, for example, the low rigidityadherend is securely adhered to the substrate in a high temperatureprocess and can be peeled after the process without being damaged ordeformed.

Preferred embodiments of the present invention have been describedhereinabove, but the present invention is not limited thereto.

For example, an aspect of the present invention relates to the use of acondensation resin having a structural unit obtained by polycondensing apolymerizable monomer containing the monomer (A) and the monomer (B),and meeting at least one of the above (1) and (2), and the above (3), asan adhesive agent.

Another aspect of the present invention relates to the use of acondensation resin having a structural unit obtained by polycondensing apolymerizable monomer containing the monomer (A) and the monomer (B),and meeting at least one of the above (1) and (2), and the above (3),for the production of an adhesive agent.

Yet another aspect of the present invention relates to the use of acondensation resin selected from the group consisting of a polyamideresin, a polyamide imide resin and a polyimide resin, and having a1,3-benzenediyl group and a polyoxyalkanediyl group, as an adhesiveagent.

Yet another aspect of the present invention relates to the use of acondensation resin selected from the group consisting of a polyamideresin, a polyamide imide resin and a polyimide resin, and having a1,3-benzenediyl group and a polyoxyalkanediyl group, for the productionof an adhesive agent.

EXAMPLES

Hereinafter, the present invention will be described in more detail withreference to examples, but is not limited thereto.

Example 1

In a separable flask equipped with a stirrer, a reflux condenser, athermometer and a nitrogen introduction tube, 50 parts (molar ratio) ofisophthaloyl dichloride, 5 parts (molar ratio) of polypropylene oxidediamine (JEFFAMINE (registered trademark) D-2000, manufactured byHUNTSMAN Corporation), and 45 parts (molar ratio) of1,4-bis(3-aminopropyl)piperazine were polycondensed under ice-cooling inN-methylpyrrolidone containing 110 parts (molar ratio) of triethylamineas an acid neutralizer. After completion of the reaction, water wasadded to the reaction mixture in an amount 3 times the amount thereofand the insoluble matter was separated and dried to obtain a polyamideresin.

Next, the obtained adhesive varnish was applied to a polyimide filmhaving a thickness of 25 μm and a width of 20 cm using an applicatorsuch that the dried adhesive layer has a thickness of 20 μm, and driedby heating at 130° C. for 5 minutes, then subsequently at 150° C. for 30minutes to prepare an adhesive material.

Example 2

In a separable flask equipped with a stirrer, a reflux condenser, athermometer and a nitrogen introduction tube, 43.75 parts (molar ratio)of isophthaloyl dichloride, 6.25 parts (molar ratio) of terephthaloyldichloride, 5 parts (molar ratio) of polypropylene oxide diamine(JEFFAMINE (registered trademark) D-2000, manufactured by HUNTSMANCorporation) and 45 parts (molar ratio) of1,4-bis(3-aminopropyl)piperazine were polycondensed under ice-cooling inN-methylpyrrolidone containing 110 parts (molar ratio) of triethylamineas an acid neutralizer. After completion of the reaction, water wasadded to the reaction mixture in an amount 3 times the amount thereofand the insoluble matter was separated and dried, to obtain a polyamideresin.

Next, the obtained adhesive varnish was applied to a polyimide filmhaving a thickness of 25 μm and a width of 20 cm using an applicatorsuch that the dried adhesive layer has a thickness of 20 μm, and driedby heating at 130° C. for 5 minutes, then subsequently at 150° C. for 30minutes to prepare an adhesive material.

Example 3

A polyamide resin, an adhesive varnish and an adhesive material wereprepared in the same manner as in Example 2, except for changing theamount of isophthaloyl dichloride added to 31 parts and the amount ofterephthaloyl dichloride added to 19 parts, in polycondensation.

Comparative Example 1

A polyamide resin, an adhesive varnish and an adhesive material wereprepared in the same manner as in Example 1, except that 50 parts ofterephthaloyl dichloride was used instead of isophthaloyl dichloride.

The weight average molecular weight of each polyamide resin obtained inExamples 1 to 3 and Comparative Example 1 was determined by thefollowing method. Further, the adhesiveness, remnants of peeling, andheat resistance of each adhesive material obtained in Examples 1 to 3and Comparative Example 1 were evaluated by the following methods. Theresults were as shown in Table 1.

(Evaluation of Adhesiveness)

The adhesive material was disposed on a 10 cm×10 cm glass plate having athickness of 70 μm and applied under a condition of 17 to 25° C. bypassing a laminator by having a roll pressure of 0.3 MPa at a rate of0.8 m/min. The edge of the polyimide film of the applied adhesivematerial was peeled slightly and held to measure the minimum strength(N/cm) required to peel off the polyimide film for a 10 mm width at anangle of 90° and a pulling speed of 300 mm/min, using a rheometerRE3305R (manufactured by Yamaden Co., Ltd.) tensile strength tester.

(Evaluation of Remnants of Peeling)

The weight of the adhesive material was measured and the weight of thepolyimide film measured in advance was subtracted therefrom, tocalculate the weight of the adhesive layer on the adhesive material.Subsequently, in the same manner as in the adhesiveness evaluation, theapplication and peeling of the adhesive material to and from a glassplate were carried out. The weight of the peeled adhesive material wasmeasured and the weight of the polyimide film measured in advance wassubtracted therefrom, to calculate the weight of the adhesive layer onthe adhesive material after peeling. At this time, the case in which theproportion of the weight of the adhesive layer after peeling is 90% ormore was referred to as “A,” and the case in which the weight proportionis below 90% was referred to as “B,” and the presence of remnants ofpeeling were evaluated.

(Evaluation of Heat Resistance)

In the same manner as in the adhesiveness evaluation, the application ofadhesive material to a glass plate was carried out. The glass plate onwhich the adhesive material was applied was heated at 200° C. in a cleanoven for one hour and visually examined for the presence of peels of theadhesive material from the glass plate. The case in which no peels werefound was referred to as “A,” and the case in which peels were found wasreferred to as “B,” and the heat resistance was evaluated.

TABLE 1 Weight average Adhesiveness Remnants Heat molecular weight(N/cm) of peeling resistance Example 1 32000 1.20 A A Example 2 525000.70 A A Example 3 35900 0.50 A A Comparative 23300 Not adhered — —Example 1 at room temperature

1. An adhesive agent comprising a condensation resin having a structuralunit obtained by polycondensing a polymerizable monomer containing amonomer (A) having 2 or more carboxyl groups and a monomer (B) having 2or more amino groups, and meeting at least one of the following (1) and(2), and the following (3): (1) at least one selected from the groupconsisting of the monomer (A), an anhydride of the monomer (A), and themonomer (B) is liquid at 25° C.; (2) the condensation resin has apolyoxyalkanediyl group; and (3) the monomer (A) contains an isophthalicacid.
 2. The adhesive agent according to claim 1, wherein the monomer(A) contains an isophthalic acid and a terephthalic acid.
 3. Theadhesive agent according to claim 2, wherein a molar ratio C1/C2 of acontent C1 of the isophthalic acid to a content C2 of the terephthalicacid in the polymerizable monomer is 1 to
 19. 4. The adhesive agentaccording to claim 3, wherein the molar ratio C1/C2 is 3 to
 19. 5. Theadhesive agent according to claim 1 meeting both of the (1) and (2). 6.The adhesive agent according to claim 1, wherein the condensation resincontains at least one selected from the group consisting of a polyamideimide resin, a polyimide resin and a polyamide resin.
 7. The adhesiveagent according to claim 1, wherein the condensation resin is apolyamide resin.
 8. The adhesive agent according to claim 1, wherein thestructural unit in the condensation resin has the polyoxyalkanediylgroup.
 9. The adhesive agent according to claim 1, wherein a structurederived from the monomer (B) in the structural unit has thepolyoxyalkanediyl group.
 10. The adhesive agent according to claim 1,wherein the polymerizable monomer contains a monomer (b-1) having apolyoxyalkanediyl group and 2 or more amino groups in a proportion of 2to 8 mol % based on the total amount of the monomer (A) and the monomer(B).
 11. An adhesive agent containing a condensation resin selected fromthe group consisting of a polyamide resin, a polyamide imide resin and apolyimide resin, the condensation resin having a 1,3-benzenediyl groupand a polyoxyalkanediyl group.
 12. The adhesive agent according to claim11, wherein the condensation resin contains an isophthalic acid unit.13. The adhesive agent according to claim 12, wherein the condensationresin further contains a terephthalic acid unit.
 14. The adhesive agentaccording to claim 13, wherein a molar ratio C1/C2 of a content C1 ofthe isophthalic acid unit to a content C2 of the terephthalic acid unitin the condensation resin is 1 to
 19. 15. The adhesive agent accordingto claim 14, wherein the molar ratio C1/C2 is 3 to
 19. 16. The adhesiveagent according to claim 11, wherein the condensation resin contains adiamine unit having a polyoxyalkanediyl group.
 17. The adhesive agentaccording to claim 11, wherein the condensation resin further has a1,4-piperazinediyl group.
 18. The adhesive agent according to claim 17,wherein the condensation resin contains a diamine unit having a1,4-piperazinediyl group.
 19. The adhesive agent according to claim 1,used as a heat resistant adhesive agent applied to an adherend andpeeled from the adherend after heated to 200° C. or higher.
 20. Theadhesive agent according to claim 1, wherein the content of thecondensation resin is 50 mass % or more.
 21. The adhesive agentaccording to claim 1, comprising the condensation resin.
 22. Use of acondensation resin having a structural unit obtained by polycondensing apolymerizable monomer containing a monomer (A) having 2 or more carboxylgroups and a monomer (B) having 2 or more amino groups, and meeting atleast one of the following (1) and (2), and the following (3): (1) atleast one selected from the group consisting of the monomer (A), ananhydride of the monomer (A), and the monomer (B) is liquid at 25° C.;(2) the condensation resin has a polyoxyalkanediyl group; and (3) themonomer (A) contains an isophthalic acid, as an adhesive agent.
 23. Useof a condensation resin having a structural unit obtained bypolycondensing a polymerizable monomer containing a monomer (A) having 2or more carboxyl groups and a monomer (B) having 2 or more amino groups,and meeting at least one of the following (1) and (2) and the following(3): (1) at least one selected from the group consisting of the monomer(A), an anhydride of the monomer (A), and the monomer (B) is liquid at25° C.; (2) the condensation resin has a polyoxyalkanediyl group; and(3) the monomer (A) contains an isophthalic acid, for the production ofan adhesive agent.
 24. Use of a condensation resin selected from thegroup consisting of a polyamide resin, a polyamide imide resin and apolyimide resin, and having a 1,3-benzenediyl group and apolyoxyalkanediyl group, as an adhesive agent.
 25. Use of a condensationresin selected from the group consisting of a polyamide resin, apolyamide imide resin and a polyimide resin, and having a1,3-benzenediyl group and a polyoxyalkanediyl group, for the productionof an adhesive agent.
 26. An adhesive material comprising a substrateand an adhesive layer containing the adhesive agent according to claim 1formed on the substrate.
 27. A method of using an adhesive agentcomprising: an application step of applying a second adherend to a firstadherend via an adhesive layer containing the adhesive agent accordingto claim 1; a heating step of heating the first adherend and the secondadherend under a condition such that a temperature of the adhesive layeris 200° C. or higher; and a peeling step of peeling the adhesive layerand the second adherend from the first adherend subjected to the heatingstep.
 28. The method according to claim 27, wherein the first adherendand the second adherend are applied at 0 to 50° C. in the applicationstep.
 29. The method according to claim 27, wherein the adhesive layerand the second adherend are peeled from the first adherend at 0 to 50°C. in the peeling step.
 30. The method according to claim 27, whereinthe adhesive layer peeled in the peeling step is reused in theapplication step.
 31. A method of using an adhesive material comprising:an application step of applying the adhesive material according to claim26 to an adherend such that the adhesive layer is disposed on the sidecloser to the adherend; a heating step of heating the adherend under acondition such that the temperature of the adhesive material is 200° C.or higher; and a peeling step of peeling the adhesive material from theadherend subjected to the heating step.
 32. The method according toclaim 31, wherein the adhesive material is applied to the adherend at 0to 50° C. in the application step.
 33. The method according to claim 31,wherein the adhesive material is peeled from the adherend at 0 to 50° C.in the peeling step.
 34. The method according to claim 31, wherein theadhesive material peeled in the peeling step is reused in theapplication step.